Monoazo-dyestuffs



Patented Feb. 9, 1954 2,668,811V MONOAZO-DYESTUFFS Heinriclrzollinger,Binningillf, Rudolf BaseL Switzerland, assignors to Ciba. Limited;

Basel; Switzerland, a Swiss firm' Y y No Drawing. Application Nrber'Z',195,1,

Serial N'.A 254,646 M l Claims priority, applicationSwitzeran-d November7, 1950 14 Claims.

l,This invention provides rrrorroazo-dyestuifs of thetypezofthefproductof the formula' tra rllhese dyestuiis correspond tothe general formula (2'5" R`1 T`=1\T"-" (ff-NLC o iz" (infwhichRgr'epresentsiafhydrogen atom; or an alkyl or` arylradical, aiidLRzvrepresents' asatu-f rated hydrocarbon radical), and Z representsaf4berizene"` radical' containing asf" aflsbstituent at least f orne-`'saturated hydrocarbon? radical l hailing@ AS] Saiii intended1atle'ast-'andfat :mosti fcarborifatom rated hydrocarbont.radicalsgj`there-ar here" alkyl"A radicals" and als'of' radicaali'cyclc series? i especiallyff'thecyloli For the productionolfftheemonaz in'gs `afi-'ven above in connection with Formulalg,"

The amino-sulfones and -amino-sulfonic l acid" amides of'theFormula3,-which are used as starting'fmaterials fin4 Ethe` present" process,-`arejnewf 'll'iey/fy can be madel by methods in'`themselves` known, frexample, by monoacylating an ap propiate i diarriho's1fon"of"diamine-sinfonia WtHahalide of anacid of the 'Orrr'viula (5) HOOC-Z Asexamples ofsutable acid halidesthere may be mentioned: 4 cyclolnzyljVbenzene 1 carboxylic acid chloride or bromide,4-sopropyl-benzene-lcarboxylic acid' chloride, 4-tertiary-amy1-benzene-ll-carbox'ylic acid chloride, Z-methyl-ljtertiary butyl"belizene 1 carboxylic acid chloride,` 26"-dimethyl#4tertiary-butyl-benzene: l-carboxylic acid' chloride,"4`n-`octy1i-benzen`el1` carboxylic acidchlrde,' or 3- or4-tertiarylbuty1`- benzene-carboxylicjacid chloride, The dia'rnies ofthe ForniulaV 4"m'ay" contain as the radical Y an aryl radical,especially an aryl radical of the benzoylamino) llf: 1"-diphen`y1sulfoneand espe dimethylor` martyr-"amide, z amino 7 i5 L 42-,

slnc acidyib'eiiyiamide, amino-544211- propylortertiarybutylbenzoylamino) -benzene l sulfonic acid -N methyl 1- phenylarnde,amino 5 (4 tertiarybutylor -cyclohexylbenzoylaminm benzenel-sulfonicAaciolliirethylzphnenylamide. These'amino-sulfones and amno--sulionicacid amdesfcanjbe; tizjefdby the methods usual forjdiazotizmgjcom ids'difficult to diazotize. foriezramplefgbyjz earl, of nitrosyl-sulfuricacid. It 'is oiten'rioffadifantageito separate the diazojsjrpriexarhieby diluting the diaz@- tizationjniizriture with vater, separatingtheccmpound lby'ltfrationjan Y, then coupling it with the ulfonic acid. Thecouacid medium, for examplefailmedimirendered;weakly acid to Congo withacetic acid. Thusyfor example, the 2- aminonaphthalene-G-mono-sulfonicacid to be used is rst converted into an alkali salt, recon- Verted intofree acid by the addition of aceticY ,Y

acid, whereby a suspension is obtained, and then causing the ltereddiaZo-compound tolcouple in this suspension. The free mineral acidresulting from the coupling reaction is then neutralized, for example,with sodium acetate and if desired the temperature is raised somewhat.The coupling mixture may be worked up in a manner in itself known, forexample, by neutralization with sodium carbonate, separation of thedyestuff by filtration and drying.

The dyestufrs obtainable by the present process are new and in the formof the free acids they correspond toY the above general Formula 2. Amongthem those of the formula especially those which contain as radical Z abenzene radical containing, preferably in p-position to the CO- group,an alkylradical having at least 3 and at most 6 carbon atoms areparticularly valuable. They are suitable for dyeing or printing a verywide variety of materials especially those of animal origin such asleather, silk and above all Wool, and also various artificial bers, forexample, those composed of animalized artificial silk, superpolyamidesand superpolyurethanes, etc. The dyeings obtained with these dyestuisare distinguished by their valuable tints and good properties offastness.

The following examples illustrate the invention, the parts andpercentages being rby weight.

Example 1 42.3 parts of Z-amino--(4"-tertiary-butylbenzoyl-amino)4-methyl-1 1diphenylsulfone are introduced into a solution ofnitrosyl-sulfuric acid in sulfuric acid corresponding to 7 parts ofsodium nitrite. When the diazotization is complete, the mixture ispoured on to ice and the precipitated yellowish diazo-compound isseparated by ltering with suction. 23.9 parts of 2-amino-8-hydroxynaphthalene-6sulfonic acid are thoroughly pasted with13.5 parts of sodium hydroxide solution of 30% strength and 20 parts ofwater, and the free acid is liberated from the resulting sodium salt bymeans of an excess of acetic acid. The diazo-compound is triturated withthe resulting paste. After a short time the whole is diluted with 200parts of water and the free sulfuric acid is slowly neutralized at amoderately raised temperature with sodium acetate. When the coupling iscomplete the whole is neutralized with sodium carbonate, and the dyestuis separated by ltration and dried. It is a dark powder which dissolvesin water with a red-violet coloration and dyes wool from an acetic acidbath Bordeaux red tints having excellent properties of wet fastness.

By using, instead of the aforesaid diazo-component, 2amino-5-(4"-tertiary-butyl-benzoylamino) -1:1diphenyl-sulfone there isobtained a dyestuir having similar properties.

The 2 amino 5 -(4" tertiary-butyl-benzoylamino)-4-methyl1:1-diphenyl-sulfone used as diam-component may be prepared asfollows:

A suspension of 26.2 parts of very nely divided 2:5diamino4methyl-1:1'diphenylsul fone in parts of water is mixed dropwiseat room temperature in the course of 2 to 5 hours with 19.65 parts ofpara-tertiary-butyl-benzoylchloride (boiling at 107-109 C. under 4 mm,pressure). By the simultaneous addition of an aqueous solution of sodiumacetate the resulting mineral acid is neutralized. In order to completethe acylation the whole is heated for a short time at about 70 C., andthen the resulting water-insoluble 2-amino 5(4-tertiary-butylbenzoyl-amino) 4-methyl-1:1diphenyl-sulfone. isseparated by filtration and dried. It is a slightly violet-grey powderand melts at 192 C.

By using in the manner described above 241i parts of2:5-diarnino-l:1diphenylsulfone, instead of 26.2 parts of2:5-diamino4methy1- 1:1diphenylsulfone, there is obtained 2-amino-5-(4tertiary butyl benzoyl amino) -1:1-di phenyl-sulfone in the form ofa violet-grey powder melting at 187190 C.

In the following table are given additional dyestuis which can be madeby the method described in the rst paragraph of this example by couplingin an acid medium the diazo-compound of an amine given in column 1 Withthe coupling component given in column 2. Certain properties of thedyestuffs so obtained are given in columns 3 and 4.

Color of Color of dyeing on Dieze-component Coupling-component solutionwool from 1n water an acetic acid bath2-am1no-5-(4-tcrtiary-butyl-benzoylamino)2-amno-8-hydroxy-naphtha1ene-6- blue-red.. blue-red.

benzene-lsulfonlc acid cyclohexylarnide. sulfonic acid.2-am1no-5-(4-tertiary-butyl-beuzoylamino) do A. do Do.

benzene-l-sullonic acid diethylamide.

Do z-aminonaphthalene--sulfonic acid.. orange.. orange.2am1no5(4-isopropyl-benzoylamino)-ben- 2-annno-S-hydroxy-naphthalene-G-blue-redl.. blue-red.

zene-lCmethyl-l: ld1phenylsulfone. sulfonic acid.2am1no5-(4-n-propyl-benzoylamino)-beudo do D0.

zene-4'methyl-l:1diphenylsulfonc.2-amiuo-5-(4cyclo-hexyl-bcnzoylamino)-bendn --.do Do.

zene-l-sulfonic acd-N-ethyl-phenylamide.2-am1no-5-(4n-propylbenzoylamino)-hendo .-.do Do.

zene-l-sulfonic acid-N-etbyl-phenylamidc.2-am1no-5-(4'-isopropyl-bcnzoylamino)-bcu dn dn Do. zene-l-sulfonicacid-N-ethyl-plienylamide.

The rst. dyestuif of this table m-l its free* acid state: corresponds"to thefformulaisoin no (lJHs mostly-Oc o-NH -N=N CHT o NH Nn nl z 10 /CHic (DSH: H2O /CHn CHi 1.5 the third to the formula SOIE l l'Hx` i.Hidec darn Nen 0H a l om Nm s-OreN.`

thefourtn to the formula SOaH H0. CH: mls-@conm- '=N- CH3 o 11TH l 2 ons40 and une. snmV to the formula-y no /CH'r-*Cga mc, CHQ-c o-NH--N=NCH2-CH2` OQ-N-CHs Example 2 45.1 parts of 2-amino-5-(4tertiarybuty1benzoylamino) -benzene-l-sulfonic acid-N-ethylphenylamide melting at4203C. are introduced into a solution of nitrosybsulfric' acid in sulfuricacid corresponding to '7" parts of sodium nitrite. When thediazotization is complete the Whole is .poured on to 1,000 to 1,200parts of ice, and the diam-compound is brought into an easily filtrableform by stirring and then separated by filtration with suction.V 25.3parts of. `2.-methy1 amino-8#hydroxynaphthaleneeSesulfonic acidarestirred with 13.5 partsof sodium hydroxide solution of 30% strength and50 parts of water; and the acid is liberated from the resulting sodiumsalt by means of anv excess of acetic acid. The diazopaste is added tothe resulting suspension, and the liberated mineral acid is neutralizedwith sodium acetate at` a moderately raised temperature, advantageouslyat about 40 C. When the 'i5 coupling` isi completev the' whole is;rendered weakly alkaline with sodium:` carbonate.. The dyestui isseparated by filtration and dried. It is a grey-violet powder whichdissolves in water with a reddish-violet coloration and dyes wool froman aceticv acid' bath somewhat reddish -brownishviolet tints having.excellent properties of wet f'astness;`

Emample 2 parts of the dyestufl" obtainable as described in the rstparagraph.. of Example 1 are dissolved in 4,000 parts4 of water, 10parts or crystalline sodium sulfate are added tothedyebath, and partsofr'wool'* are enteredl at 1o-50" C'. There are then added" 3 parts' ofaceticacidp of" 40 strength, the whole is raised to the' boil: inthecourse of half an hour and dyeingl is carried on for of an hourat thattemperature: After rinsing and drying the material a' fast Bordeaux reddyeing is obtained.

What is claimed is:

1. A monoazo-dyestuff which in the form of the free acid correspondstothe formula SOJH and NH-X, X being a saturated hydrocarbon radical.

2. A monoazo-dyestuf which in the form of the free acid correspondstothe formula- SiOaH i 3. A monoazo-dyestuff which in the form of the freeacid corresponds to the formula SOSH SOaH

wherein n stands for a whole number which is at most 2, Z represents abenzene radical containing at least one alkyl group of at least 3 and atmost 8 carbon atoms, R4 and R5 represent alkyl groups of low molecularWeight.

5. A monoazo-dyestuff which in the form of the free acid corresponds tothe formula SIOaH wherein 1t stands for a Whole number which is at most2, Z represents a benzene radical containing at least one saturatedhydrocarbon group of at least 3 and at most 8 carbon atoms, R4represents an alkyl group of low molecular weight and R5 a benzeneradical.

6. A monoazo-dyestui which in the form of the free acid corresponds tothe formula SOaH wherein Re represents an alkyl radical containing atleast 3 and at most 8 carbon atoms and Y represents a benzene radical.

7. A monoazo-dyestui which in the form of the free acid corresponds tothe formula OLNERI NH:

wherein Rs represents an alkyl radical containing at least 3 and at most8 carbon atoms and R4 represents a cyclohexyl radical.

8. A monoazo-dyestuff which in the form of 5 the free acid correspondsto the formula SOxH son-ll-Ih NH: Rs

wherein Re represents a saturated hydrocarbon radical containing atleast 3 and at most 8 carbon atoms and R4 represents an alkyl radicalcontaining up to 6 carbon atoms and R5 represents a benzene radical.

9. A monoaZo-dyestuf which in the form of the free acid corresponds tothe formula SQIH Re l wherein Rs represents an alkyl radical containingat least 3 and at most 8 carbon atoms and R4 and R5 each represent alkylradicals containing up to 6 carbon atoms.

10. The monoazo-dyestufl which in the form of the free acid correspondsto the formula l1. The monoazo-dyesturf which in the form of the freeacid corresponds to the formula 9 10 12. The monoazo-dyestui which inthe form 13. The monoazo-dyestui which in the form of the free acidcorresponds to the formula of the free acid corresponds to the formulaSloan S 01H HO 5 (IJH om HC"(f`'c O`NHN=N Hide- 3@ o-NH -N=N CH: SOWNHNH, H3 01H5 il 10 s N/ NH; 0H 1- HaC/ \(|}Hs 1 03H5 H.\ /CHs 14. Themonazo-dyestutf which in the form CH, of the free acid corresponds tothe formula.

OPN-02H5 NH:

HEINRICH ZOLLINGER. RUDOLF RUEGG.

References Cited in the le of this patent UNITED STATES PATENTS NumberName Date 1,840,385 Clingestein et a1. Jan. 12, 1932 2,505,268 WidmerApr. 25, 1950

1. A MONOAZO-DYESTUFF WHICH IN THE FORM OF THE FREE ACID CORRESPONDS TOTHE FORMULA